Process for breaking petroleum emulsions



Patented June 24, 1930 1 7 UNITEDSTATES PATENT OFFICE -IMIELVIN' DE GROOTEOF ST. LOUIS, AND LOUIS T. MONSON, OF MAPLEWOOD, MISSOURI, ASSIGNORS TO S. BARNIGKEL & COMPANY, OF WEBSTER GROVES, MISSOURI, -A CORPORATION OF MISS URI I PROCESS FOR BREAKING PETROLEUM EMULSIONS No Drawing.' Application filed'J'anuary 21, 1929. Serial No. 334,114.

This invention relates to the treatment of detail by stating that it is a sulfonic petroemulsions of mineral oil and water, such leum condensation product derived from a as petroleum emulsions, for thepurpose of petroleum 7 body, characterized by being separatingtheoil from the water. chemically reactive towards sulfuric acid.

5 Petroleum emulsions are of the water-inand a ketone having fewer than fourteen 50 oil type and comprise fine droplets of natucarbons. As a petroleum'body wecan emrally-occurring waters or brines, dispersed ploy any raw or purified oil which is capable in a more or-less permanent state throughout 'of reaction with sulfuric acid to give a sulthe oil which constitutes the continuous fate or sulfonate. Likewise, we can employ 10 phase of the emulsion. They are obtained any material which is already a sulfonic 55 from producing wells, and from the bottoms acid or a petroleum acid sulfate. -A suitof oil storage tanks and are commonly reable material is a petroleum sulfonic acid, ferred to as cut oil, roily oil, emulsified such as is obtained by the action of sulfuric 011,? and bottom settlings. acid or oleum oncrude petroleum or its fracv The object of our invention is to provide tions, or on a material obtained by pyrolytic 60 a novel and. inexpensive process for sepaaction, such as material obtained from rating emulsions of the character referred cracking stills. Another suitableliquid ma-v to into their component parts of oil and terial is the petroleum body obtained by water or brine. extraction of raw petroleum or=other frac- .Briefly described, our process consists in 'tions with liquid sulfur dioxide. A desir- 65 subjecting a petroleum emulsion of the able raw material may be obtained by parwa-ter-in-oil type to the action'of atreating tialtoxidation of selected petroleum bodies. agent or demulsifying agent of the kind A carboxylic material of the designated hereinafter described, thereby causing the specification is also satisfactory. Another emulsion to break down and separate into suitable material is residual oil obtained 70 its component parts of oil and water or brine, from cracking stills, which is in essence a when the emulsion is permitted to remain mixture of high boiling cyclic bodies simin a quiescent state after treatment. ilar to aromatic bodies. -Briefly then, the

The treating agent employedin our proc petroleum body employed may be a crude [3b ess. consists of a petroleum sulfonic body oil or a fraction thereof, or a material de- 7 derived from'thecondensation of a petrorived from a cracking process, and is adaptleum body, characterized by being capable able to our purpose, provided it is asulfonic of reaction with sulfuric acid, and a ketone. body or capable of entering into reaction It is produced by the action-10f a condensing with sulfuric acid to give a. sulfonic acid and sulfonating agent on the petroleum body 'oracid sulfate. 80

hereinafter described, and a ketone having The ketone employed in the manufacture fewer thanfourteen carbon atoms. In man or production of our treating agent maybe ufacturing or ,producing said treating agent, an aliphatic ketone, such'as acetone, methyl- 4.

we do not contemplate using all kinds of ethylketone, diethylketone, or dipropylke petroleum? bodies. On the contrary, we use tone. Likewise, an aromatic ketone, such as 5 i only those petroleum bodie's that are capable benzopheno'ne, or an aromatic-aliphatickeof being united with sulfuricacid to give tone, such as acetophenone, may be emchemical compounds,. such as acid sulfate, ployed. p

. orsulfonic acids; We will define our treat The general method fused to produce the ing agent :or demulsifying agent more in treating agent s to mix a selected petroleum t0 line earth salts.

body and a ketone body in predetermined ratios, such as molecular proportions, and subject the mixture to the action of a condensin agent and a sulfonating agent, such as sul uric acid. Obviously, if the petroleum body is a petroleum sulfonic acid, it is only necessary to obtain condensation, inasmuch as the sulfonic acid radical is already present. It is possible to introduce two or more ketone residues into.the petro leum body. The ketones employed may be tion of the kind described more than one.

sulfonic group can be introduced into the petroleum body. In addition toa ketone' residue, an alcohol residue, or aldehyde residue or fatty residue may also be introduced into the petroleum body.

The procedure that we prefer to use in producing the treating agent or demulsifying agent contemplated by one process is as follows: Two moles of dipropylketone are mixed with one mole of a petroleum sulfonic acid, and agitated vigorously, with v careful addition of sulfuric, acid. The temperature is allowed to rise and excess acid is added until condensation is complete. At times, it may be necessary to add a small amount of oleum or chloro-sulfonic acid to complete the final condensation. Sometimes," a suitable catalyst such as a phosphorus compound may be employed. When reaction is complete, the mass is diluted with water until an upper layer separates. upper layer is drawn off and neutralized with any suitable base, such as caustic soda, caustic potash, orammonia. We preferto use ammonia.

Our broad idea contemplates the use of.

a treating agent havingthe general characteristlcs pointed out, produced in various ways. The treating agent that we prefer to employ, however, is one, that produces an insoluble precipitate with soluble alka- The presence or absence of such precipitate probably depends'on the number of sulfonlc acid groups introduced I into the petroleum body. Therefore, it is our preference that the reaction be carried on, so that the product of thereaction will show insolubility with alkaline earth salts y a su ta le t t u a the t l ns A The 1% solution of the reagent is mixed with a 1% solution of magnesium sulfate and heated for 10 to 30 minutes in a water bath just below the boiling point of water, if required. In the test with either the calclum salt or the magnesium salt, a precipitate should be obtained which remains after the mixture is diluted with two times its volume .of distilled water.

A material or substance of the kind above described can be employed as an acid mass to treat a. petroleum emulsion, but this is not desirable, due to its corrosive effect. There is no objection to an excess .of alkali, if desired. Such material can also be converted into an ester by esterification in the usual manner to produce an aromatic or aliphatic ester such as the ethyl ester. Some of the esters so produced may be oilsoluble, such as the hexyl ester.

The treating agent, when it is ready for use, may be acidic in nature, and the complex substituted etroleum'sulfonic group may be united with an acid hydrogen ion, as isthe case when the acid itself is employed. When said acidic material is neutralized, the hydrogen ion is replaced by a suitable metallic ion equivalent, such as a true metallic ion or an ammonium radical.

,In the event that the material is esterified,

the hydrogen ion isreplacedby an organic radical, such as an ethylradical. We will refer to the hydrogen ion or its metallic substitute or its organic substitute as the hydrogen ion equivalent.

The form, state or condition of the treating agent at the time it is mixed with or applied to the petroleum emulsion to be treated, may be varied to suit existingconditions. It ,can be used in substantially anhydrous state or in solutions of any convenient strength. A concentrated solution can be emulsified into oil by agency ofany suitable oil-soluble emulsifier, such as calcium oleate. The treating agent can be formed entirely from a material .of the kind previously described, or it can be formed from such a materlal in combination with other well-known treating agents for petro- In practicing our process a treating agent or demulsifying agent of the kind above described may be brought'in contact withv the emulsion to be treated in any of the numerous ways now employed in the treatmentof petroleum emulsions of the waterin-oih type with chemical d'emulsifying agents, such, 'for example, as by introducing the treating agent-into-the Well in which the emulsion is produced; introducing the twel lng agent into a conduit through which the emulsion is flowing; introducing the treating agent into a tank in which the emulsion is stored, or introducing the treating agent into a container that holds a sludge obtained from the bottom of an old before said water and oil enter the barrel of the well pump or the tubing up through which said water and oil flow to the surface of the ground.

. After treatment the emulsion is allowed to stand in a quiescent'state, usually in a settling tank, at a temperature varying from atmospheric temperature to about 200 F., so as to permit the water or brine to separate from the oil, it being preferable to keep the temperature low enough so as to prevent the valuable constituents of the oil from volatilizing; If desired, the treated emulsion may be acted upon by one'or the other of various kinds of apparatus now used in the operation of breaking petroleum emulsions, such as hom'ogenizers, hay tanks, gun barrels, filters, centrifuges or electrical dehydrators.

The amount of treating agent on the anhydrous basis that is required to break the emulsion may vary from approximately 1 part of treating agent to 500 parts of emulsion, up to a ratio of 1 part of treating agent to 20,000 parts of emulsion, depending upon the type or kind-of emulsion being treated. In treating exceptionally refractory emulsions of the kind commonly referred to as tank bottoms or residual pit oils, the minimum ratio above referred to is often necessary, but in treating fresh emulsions, i. e., emulsions that will yield readily to the action of chemical demulsifying agents, the maximum ratio above mentioned will frequently produce highly satisfactory results. For the average petroleum emulsion of the water-in-oil type 'a ratio of 1 part of treating agent to 5,000 parts of emulsion will usually be found to produce commercially satisfactory results.

Having thus described our inventidn, what we claim as new and desire to secure by Letters Patent is:

1. A process for breaking a petroleum emulsion of the 'water-in-oil type, which consists in subjecting the emulsion to the action of a demulsifying agent containing a petroleum-sulfonic body derived from the condensation of a petroleum body, characterized by being capable of reaction with sulfuric acid, and a ketone.

2. A process for' breaking a petroleum emulsion of the water-in-oil type, which consists in subjecting the emulsion to the action of a water-soluble demulsifying'agent containing a petroleumsulfonic'body derived from the condensation of a petroleum body, characterized by being capable of reaction with sulfuric acid, and a ketone.

3. A process for breaking a petroleum emulsion of the water-in-oil type, which consists in subjecting the emulsion to the action of a water-soluble demulsifying agent containing a water-soluble salt of a petroleum sulfonic body derived from the condensation of a petroleum body, characterized by being capable of reaction with sulfuric acid,

and a ketone.

4. A process for breaking a petroleum emulsion of the water-in-oil type, which consists in subjecting the emulsion to the action of "a water-soluble demulsifying agent containing an ammonium salt of a petroleum sulfonic body derived from the condensation of a petroleum body, characterized by being capable of reaction with sulfuric acid, and a ketone.

5. A process for breaking a petroleum emulsion of the water-in-oil type, which consists in subjecting the emulsion to the action of a demulsifying agent containing'a petroleum sulfonic body derived from the condensation of. a petroleum body, characterized by being capable of reaction with sulfuric-acid, and an aliphatic ketone..

6. Aprocess for breaking a petroleum emulsion of the water-in-oil type, which consists in subjecting the emulsion to'the action of a water-soluble demulsifying agent containing petroleum sulfonic body derived from the condensation of a petroleum body, characterized by being capable of reaction with sulfuric acid, and an aliphatic ketone.

7. A process for breaking a petroleum emulsion of thewater-in-oil type, which consists in subjecting the emulsion to the action of a water-soluble demulsifying agent containing a water-soluble salt of a petroleum sulfonic body derived from the condensation of a petroleum body, characterized by being capable of reaction with sulfuric acid, and an aliphatic ketone.

8. A process for breaking a-petroleum emulsion of the water-in-oil type, which consists in subjecting the emulsion to the action of a water-soluble demulsifying agent containing an ammonium salt of a petroleum sulfonic body derived from the condensation of a petroleum body, characterized by being capable of reaction with sulfuric acid,and an aliphatic ketone.

9. A process for breaking a petroleum emulsion of the water-in-oil type; which consists in subjecting the emulsion to the actionk of a demulsifying agent containing a petroleum sulfonic body. derived from the condensation ofa petroleum body, characterized by being capable of reaction with sulfuric acid, and an aliphatic ketone, and

furthermore, characterized by producing a precipitate with an alkaline earth salt.

10. A process for breaking a petroleum emulsion of the water-in-oil type, which con-' sists in subjectingthe emulsion. to the action of a water-soluble demulsifying agent containing a petroleum sulfonic body derived from the condensation of a petroleum body, characterized by being capable of reaction with sulfuric ,acid, andanaliphatic ketone,

and furthermore, characterized by producing a precipitate with an alkaline earth salt. 11. A process for breaking a petroleum emulsion of the water-,in-oil type, which con-1 sists in subjecting the emulsion'to the action of a water-soluble demulsifying 'agentcontaining a water-soluble salt of a petroleum sulfonic body derived from the condensation of a petroleum body, characterized by being capable of'reaction with sulfuric acid, and

analiphatic ketone, and furthermore, characterized by producing a precipitate-with an alkaline earth salt.

12. A process for breaking a petroleum emulsionof the water-in-oil type, which consists in subjecting the emulsion to the action of a water-soluble demulsifying agent containing an ammonium salt of a petroleum sulfonic body derived from the condensation of a petroleum body, characterized by being capable of reaction with sulfuric" acid, and an aliphatic ketone, and furthermore, characterized by producing a precipitate with an alkaline earth salt. j

.13. A process for breaking a petroleum emulsion of the water-in-oil type, which consists in subjecting the emulsion to'the action of a demulsifying. agent containing a petroleum sultonic body derived from the condensation ofa'petroleum body, characterized by being capable of reaction with sulfuric acid, and dipropylketone, and furthermore characterized by producing a precipitate with an alkaline earth salt.

14. A process for breaking a petroleumemulsion of the water-in-oil type, which consists in subjecting the emulsion to the action of a water-soluble demulsifying agent containing a petroleum sulfonic body derived I from the condensation of a petroleum body, characterized by being capable of reaction with sulfuric acid, and dipropylketone, and

furthermore characterized by producing a precipitate with an alkaline earth salt.

15. A process for breaking apetrole'um 'emulsionof-the water-in-oil type, which consists in subjecting the emulsion to the action of a water-soluble demulsifying agent containing a water-soluble salt of a petroleum sulfonic body derived from the condensation of a, petroleum body, characterized by bein capable of reaction with sulfuricacid, an dipropylketone, and furthermore characterized byproducing a precipitate with-an alka-z-v 16. A process for breaking a petroleum 

